journal of Chromatographic Science, Vol.

36, May 1998

Analysis of Dissolved Methane, Ethane, and

Ethylene in Ground Water by a Standard
Gas Chromatographic Technique
Don H. Kampbell*
U.S. Environmental Protection Agency, National Risk Management Research Laboratory, P.O. Box 1198, A d a , O K 7 4 8 2 0

Steve A. Vandegrift
ManTech Environmental Research Services Corporation, National Risk Management Research Laboratory, P.O. B o x 1198, A d a , O K 7 4 8 2 0

Abstract
The measurement of dissolved gases such as methane, ethane, and
ethylene in ground water is important in determining whether
intrinsic bioremediation is occurring in a fuel- or solventcontaminated aquifer. A simple procedure is described for the

need was for a simplified, rapid technique using readily available

equipment to analyze ground water samples simultaneously for
methane, ethane, and ethene. Previously, we reported on a gas
chromatography (GC) headspace technique that emphasized dis
solved oxygen (6). In recent years, the emphasis has been on
methane and ethene analysis in water.

collection and subsequent analysis of ground water samples for

these analytes. A helium headspace is generated above a waterfilled bottle. Gases that are dissolved in the water partition
between the gas and liquid phases and equilibrate rapidly. An

Experimental

aliquot of this headspace is analyzed by gas chromatography to

determine the gases' concentration in this phase. The concentration
of the gas dissolved in the water can then be calculated based on
its partitioning properties, as indicated by its Henry's Law constant.

Introduction
Our involvement in ground water sampling and analyses at
fuel and/or chlorinated solvent spill sites has required the deter
mination of dissolved methane, ethane, and ethene. These con
stituents are frequently used to detect biodegradation processes
in contaminated aquifers. Presence of the compounds is used to
determine whether natural processes of contaminant attenua
tion and destruction are occurring at a spill site (1). Under anoxic
conditions, the bioremediation processes for fuel hydrocarbons
shift toward methanogenesis, which forms methane. Under sim
ilar conditions, chlorinated solvents such as trichloroethylene
are subjected to reduction dechlorination; the final products are
ethene and chloride (2).
Techniques for the analysis of dissolved gases in water have
included direct aqueous injection into a GC equipped with a
flame-ionization detector (FID) (3), membrane inlet mass spec
trometry (4), and near-infrared Raman spectroscopy (5). Our
* Author to whom correspondence should be addressed.

Materials
Gas standards in helium were obtained from Scott Specialty
Gases (Plumsteadville, PA). "Scotty II" cylinders of methane,
ethane, and ethene at 10, 100, and 1000 ppm were used in addi
tion to standards of methane at 1, 10, and 20%. High-purity
helium was used as the GC carrier and as a source to prepare
headspace in the sample bottles.
Instrumentation
Samples were analyzed using a Hewlett-Packard (Palo Alto,
CA) 5890 GC equipped with a packed column (6-ft1/8-in.
Porapak Q, 80/100) and an FID. The carrier gas was high-purity
helium at 20 mL/min. The oven was programmed with an initial
temperature of 55C for 1 min, increased at 20C/min to 140C,
then held for 5 min. The injector was set at 200C, and the FID
was set at 250C. The FID hydrogen was set at 40 mL/min, and
the air flow was set at 400 mL/min. The FID range and attenua
tion were both at 0. An HP 3396 Series II integrator was used for
signal acquisition and peak integration.
Sample collection and preparation
Water samples from field monitoring wells were collected into
60-mL serum bottles (Wheaton, Millville, NJ). Water was gently
added down the side of the bottle so as not to agitate or create
bubbles, which could strip gases dissolved in the water. The

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Journal of Chromatographic Science, Vol. 36, May 1998

bottle was completely filled, and several drops of 1:1 sulfuric acid
were then added as a preservative. The bottle was capped and
sealed using a 20-mm gray butyl rubber, Teflon-faced septum
(Wheaton, Millville, NJ) and 20 mm aluminum crimp seal
(Wheaton). The samples were kept cold in an ice chest in transit
to the laboratory. Samples were kept at 4C and analyzed within
14 days of collection.
GC analysis
The GC was calibrated by injecting 300 L of each of the gas
standards as listed in the Materials section. The Scotty II cylin
ders were sampled at atmospheric pressure. This was accom
plished by attaching a short piece of1/4-in.stainless steel tubing
with appropriate fittings to the cylinder outlet. At the cylinder
outlet, a1/4-in."tee" was fitted with a GC septum allowing for
insertion of a gas-tight syringe needle into the gas stream. The
exit end of the tubing was inserted into a 500-mL beaker of water.
As gas "bubbled" through the water, 300 L of the gas standard
was removed and injected into the GC. The retention times for
methane, ethene, and ethane were near 0.6, 1.9, and 2.5 min,
respectively. Peak area counts generated for each sample were
compared with a calibration standard curve.
Samples were allowed to reach room temperature prior to
analysis. A headspace was prepared by replacing 10% of the bot
tled sample (in this case, 6 mL) with helium. To generate
headspace in the sample bottle, the bottle was placed upsidedown in a three-fingered clamp attached to a ring stand. Next, a
20-gauge needle attached to a 10-mL Luerlok glass syringe set
for dead volume was inserted through the septum. Then an 8-cm
20-gauge needle attached to Teflon tubing and a needle valve was
inserted through the septum up to the bottom of the bottle. The
Teflon tubing was plumbed to a two-stage regulator on a cylinder
of high-purity helium, and the helium was passed through the
needle at 5 mL/min or less. The helium forced water out of the
bottle and into the syringe. When the volume of water in the
syringe reached 6 mL, the 8-cm needle was pulled out, followed
by the syringe. The sample bottle was shaken on a rotary shaker
at 1400 rpm for 5 min to allow the gases to equilibrate between
the headspace and liquid phases.
A 500-pL gas-tight syringe with a sampling valve (Dynatech
Precision Sampling, Baton Rouge, LA) and equipped with a sideport needle was used to withdraw 300 L of headspace, which
was subsequently injected into the GC. The temperature of the
remaining sample was determined. The volume of the sample
bottle was measured by filling the bottle with water and pouring
the contents into a graduated cylinder.
For purposes of quality control, field trip blanks were included
with samples, and 10% of samples were collected in duplicate
and analyzed. Prior to analysis and at the end of the day, calibra
tion of the GC was checked by analyzing at least one of the gas
standards for each analyte. The GC was considered to be in cali
bration if the analyzed value was within 15% of that expected.
Calibration standards for at least one of the gases were analyzed
with a frequency of 10%. Control charts were maintained to
monitor variability. In addition, a method blank consisting of a
serum bottle of deionized, boiled water was analyzed on a daily
basis. This was necessary to correct for background levels of
methane. Quantitation limits for methane, ethane, and ethene
254

were 0.001, 0.002, and 0.003 mg/L, respectively. Normally, two

samples could be prepared and analyzed per hour.
Calculations
The concentrations of the gases dissolved in the water sample
were calculated using the partial pressure of the gas, Henry's Law
constant, the temperature of the sample, the volume of the
sample bottle, and the molecular weight of the gas. Values for
Henry's Law constant were obtained from Perry's Chemical
Engineer's Handbook (1).
The linear regression equation of the standard curve was used
to determine the partial pressure (p ) of the gas. The concentra
tions of the gas standards should be converted to their decimal
equivalent before generating the curve (i.e., 10 ppm is equivalent
to 0.00001, as is 1% to .01). The sample's area count obtained
from the chromatogram peak for the analyzed gas was "inserted"
into the equation to determine its partial pressure. For methane,
it was necessary to subtract the area count obtained from the
analysis of a method blank. The following sequence of equations
were used to determine the concentration of the dissolved gas.
For the equilibrium mole fraction of the dissolved gas:
g

Eq 1
where H is Henry's Law constant for the gas. Let n represent the
moles of gas and n the moles of water. Then:
g

Eq 2
Because 1 L of water equals 55.5 g-moles:
Eq 3
and because:
Eq 4
therefore:
Eq 5
For the saturation concentration of the gas:
Eq 6
where MW is the molecular weight of the gas. To correct gas der
sity for temperature:
Eq 7
where ST is the sample temperature. Then:
Eq 8

where A is the milliliters of analyte in the headspace. Then:

h

Eq 9

Journal of Chromatographic Science, Vol. 36, May 1998

where A is the analyte in liquid phase and V is the volume of

water (bottle volumeheadspace volume) in L; using a 60-mL
serum bottle with 6 mL of headspace, V equals 0.054 L. Then:
I

Eq 10
where TC is the total concentration of analyte in the original
sample, in milligrams of gas per liter of water.
Example calculation for methane
Methane will be used as an example of the calculations used
for the analysis of dissolved gases. From the analysis of a sample,
an area count was determined. This area count was used in the
equation for the linear regression of the calibration curve to give
its partial pressure (p ). Parameters used for this example are as
follows: the sample area count was 978264, the method blank
area count was 2766, Henry's Law constant was 4.13E+4 (at
25C), the sample temperature was 25C (298K), the bottle
volume was 60 mL, and the headspace volume was 6 mL.
From the equation of a straight line (y=mx+ b), the calibra
tion standard responses generated the following curve:

A typical chromatogram of a ground water sample from a con

taminated site is shown in Figure 1. Table I lists the analytical
data for several water samples. Calibration curves were gener
ated using linear regression on a calculator or computer; area
counts of the standards were plotted versus their concentrations.
Saturated solutions of methane and ethene in water were pre
pared with expected concentrations of 22.7 and 131 mg/L,
respectively. They were analyzed to determine precision and
accuracy. For methane, an average recovery of 87% was obtained
for six replicates, the standard deviation was 0.64 mg/L, and the
relative standard deviation (RSD) was 3.25%. For ethene, the

Eq 11
Therefore, for this sample:
Eq 12

Then, using the previous equations:

(from Eq 1)
(from Eq 5)

(from Eq 6)

(from Eq 8)

(from Eq 10)

Results and Discussion

Water samples collected at field sites have been analyzed by
the described procedure for over eight years. The method is
relatively simple and reliable for the analyses of water samples.

Figure 1. Typical chromatogram of a field sample. Retention times for

methane, ethene, and ethane were 0.635, 1.955, and 2.458 min, respectively.

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Journal of Chromatographic Science, Vol. 36, May 1998

Table I. Analytical Data of Four Samples from a Field Site

Methane

Ethene

Ethane

(mg/L)

(mg/L)

(mg/L)

RW-10

0.682

undetected

0.027

RW-11

4.753

undetected

0.219

RW-12

1.268

undetected

0.013

RW-12*

1.260

undetected

0.013

RW-13

3.074

0.268

0.112

3.143

0.258

0.107

Sample

RW-13

Acknowledgments
The authors are grateful to Bryan Newell and Jeff Hickerson of
ManTech Environmental Research Services for their support as
analysts. Pat Holt of National Risk Management Research
Laboratory typed the manuscript. The research described has not
been subjected to a review process by the United States
Environmental Protection Agency. Therefore, the work does not
necessarily reflect the views of the agency, and official endorse
ment should not be inferred.

* Lab d u p l i c a t e (i.e., headspace of same s a m p l e a n a l y z e d twice).

Field d u p l i c a t e .

average recovery for three replicates was 90%, the standard devi
ation was 8.8 mg/L, and the RSD was 7.5%. Due to the unavail
ability of pure ethane in our lab, this exercise was not performed
on ethane.
With appropriate GC detectors, this technique should be appli
cable to other volatile dissolved constituents in water such as
carbon dioxide, nitrous oxide, nitrogen, and vinyl chloride. It
should be noted that acid preservation should not be used for
carbon dioxide analysis because inorganic carbon may be con
verted to carbon dioxide.

References
1.

2.

3.

4.

Conclusion

5.

The sample preparation and analytical technique for dissolved

methane, ethane, and ethene in ground water has been used suc
cessfully on a routine basis in our lab. We have analyzed thou
sands of ground water samples from numerous contaminated
sites. The data from these analyses have been critical in deter
mining the nature of the degradative processes in contaminated
aquifers. This technique will continue to be used for routine
analyses on water samples from both lab and field studies.

256

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7.

Manuscript accepted December 11, 1997.